Soft touch laminates constructed with improved fire retardant properties for transportation

ABSTRACT

Soft touch fire retardant laminates with PVC middle layers, foamed or unfoamed, and multiblock copolymer or polyurethane or silicone top layers which meet FAA requirements are disclosed.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of co-pending U.S. application Ser.No. 14/213,554 filed Mar. 14, 2014, which in turns claims the benefit ofU.S. Provisional Application No. 61/782,907, filed Mar. 14, 2013, all ofwhich are incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to multi-layered laminates for use insurface covering applications having improved fire retardant properties.These materials have the look and feel of leather with a greaterresistance to burning than presently available soft touch laminates.

BACKGROUND OF THE INVENTION

While “Soft-Touch”/“Soft-Feel” leather like materials are well known inthe art, the traditional products have undesirable burn properties whenused in commercial transportation (for upholstering or coveringsurfaces; i.e. they readily burn and/or give off toxic fumes/smoke.Current “soft-touch” products for general use (automotive, consumerproducts, etc.) readily burn or melt and produce toxic smoke. Incommercial aviation there are even fewer options; due to the stringentregulatory requirements designed to protect passenger safety in theevent of a fire. Synthetic leathers make up the majority of what isused. These often have marginal burn properties which limits where andhow they can be used. Additionally many have poor durability and staineasily.

The art has tried to address this by using fire resistant silicones.Silicone products have been developed that can be used for a soft feeland some of them can meet aviation requirements. However these siliconesfeel “sticky” or “tacky” and while soft, are generally not mistaken forleather. Additionally, because of the stickiness, silicones can pick upand retain dirt and stains.

Further, other soft feel products do not have great damageresistance/durability rendering them unsuitable for high wear areas suchas aircraft or other interiors or had a soft feel but lacked thecompressive quality or could not pass the burn requirements.

DESCRIPTION OF THE DRAWING FIGURES

FIG. 1 is a schematic representation of a first embodiment of a laminateof the present disclosure;

FIG. 2 is a schematic representation of a second embodiment of alaminate of the present disclosure;

FIG. 3 is a schematic representation of a third embodiment of a laminateof the present disclosure, and

FIG. 4 is a schematic representation of a fourth embodiment of alaminate of the present disclosure.

DETAILED DESCRIPTION OF PREFERRED AND ALTERNATE EMBODIMENTS

The present invention is an engineered high performance decorativelaminate that has a soft feel, for example like leather or syntheticleather. It will meet or exceed all Federal Aviation Administration(“FAA”) regulations. Specifications for fire, smoke and toxic gases foruse in all areas of commercial aircraft are considered. It will alsohave excellent stain resistance and durability. By coating a poly(vinylhalide) or a poly(vinylidene halide) film with a flame retardedmultiblock copolymer and optimizing this layer for feel and burn theselimitations were overcome.

“Multiblock copolymers” as used herein include polyurethanes (PU),copolyamides (COPA), copolyesters (COPE), and styrenics such as SIS,SBS, SIBS and the like. These copolymers are preferably cross-linkablethermoplastics or thermosets.

“Poly(vinyl chloride)” or “PVC,” as used herein, includes homopolymersof vinyl chloride, as well as polymerization products of vinyl chlorideand one or more co-monomers. For example, the PVC resin can be acopolymer of vinyl chloride and ethylene, or a copolymer of vinylchloride and propylene. The PVC resin can also be the polymerizationproduct of vinyl chloride and an ester monomer having formulaH₂C═C(R¹)OC(═O)R² or H₂C═C(R¹)C(═O)OR², where R¹ and R² are,independently, C₁₋₁₂ alkyl. An example of such a resin is a copolymer ofa vinyl chloride monomer and a methyl methacrylate monomer. Anotherexample of such a resin is a copolymer of a vinyl chloride monomer and avinyl acetate monomer. Combinations of these PVC resins may also beused.

“Poly(vinylidene fluoride)” or “PVDF,” as used herein, includeshomopolymers of vinylidene floride, as well as polymerization productsof vinylidene fluoride and one or more co-monomers. For example, thePVDF resin can be a copolymer of vinylidene fluoride andhexafluoropropylene, or a copolymer of vinylidene fluoride andchlorotrifluoroethylene. The PVDF resin can also be the polymerizationproduct of vinylidene fluoride and an ester monomer having formulaH₂C═C(R¹)OC(═O)R² or H₂C═C(R¹)C(═O)OR², where R¹ and R² are,independently, C₁₋₁₂ alkyl. An example of such a resin is a copolymer ofa vinylidene fluoride monomer and a methyl methacrylate monomer. Anotherexample of such a resin is a copolymer of a vinylidene fluoride monomerand a vinyl acetate monomer. Combinations of these PVDF resins may alsobe used. Blends of PVDF with other polymers can also be used, forexample PVDF/acrylic blends.

“Prepreg” are coatings in which polymers such as PET, PPS, and PEEK aresuspended in an organic liquid, optionally with flame retardants.

“Silicone foam” is a silicone material containing open and/or closedcells and are available from a variety of manufacturers. Foams areavailable in a wide variety of durometers and with glass backing fordurability. Specifically selected and designed systems with improvedflame retardant properties beyond the natural flame retardant propertiesof silicone based materials is required to meet the intent of theinvention.

“Organosols” are coatings in which PVC is suspended in an organic liquidoptionally with flame retardants.

Suitable adhesives and primers include, but are not limited to: phenolicresins, polyesters, epoxies, polyurethanes, and methacrylics. Becausethe adhesives need to be compatible with the materials they are bondingand provide the requisite strength for the application, typically themanufacturer of the laminate layer will specify which adhesives orprimers are compatible in use with their products.

The compositions contain one or more flame retardant or combinations offlame retardants. The flame retardants can be liquid or solid. Preferredflame retardants include but are not limited to aluminum trihydroxide,available from various suppliers, including Alcoa, under the productname Hydrated Aluminas; magnesium hydroxide, available from varioussuppliers, including Albermarle, under the trade name MAGNIFIN (e.g.,Magnifin H-10 or Magnifin H-5); flame-retardant plasticizer such asphosphate ester plasticizers, available from various suppliers,including Ferro, under the trade name SANTICIZER (e.g., Santicizer2148), tetrabromophthalates, polymeric plasticizers (for example, Admix412, available from Teknor Apex), combinations of bromo andchlorophthalates (for example, Unitex 44-55), and chlorinatedhydrocarbons (for example, Cercelor S52); and ammonium octamolybdate,available from various suppliers, including Polymer Additives Group,under the trade name Climax AOM; Alkyl aluminum phosphonates andphosphinates such as AMMP and DEPAL sold by ICL-IP and Clariant,respectively, zinc sulfides, sold by Sachtleben, zinc borates sold by USBorax Inc, and zinc hydroxy stannates sold as ZS 286 by 3NInternational; bismuth oxide, sold by 3N International. Additional flameretardants are described in Linsky et al., U.S. Pat. No. 5,886,072, andShtekler et al., WO 2012/088080, which are hereby incorporated byreference in its entirety. The compositions preferably include at leastabout 50 parts total flame retardant per 100 parts polyvinyl chlorideresin, and more preferably from about 50 parts to about 200 parts totalflame retardant per 100 parts polyvinyl chloride resin. The compositionmay include, for example, from about 5 parts to about 60 parts, fromabout 10 parts to about 50 parts, or from about 20 parts to about 40parts flame retardant plasticizer per 100 parts polyvinyl chlorideresin.

In one embodiment of the present invention, as schematically illustratedin FIG. 2, the laminate comprises a top layer of clear flame retardedmultiblock copolymer film bonded to a clear poly(vinyl halide) or apoly(vinylidene halide) film, optionally containing fire retardants.This laminate is then bonded to a flame retarded PVC layer containingpigments and flame retardants. It may be necessary to use a primer inorder to attain good adhesion between the laminate and the PVC layer.These layers are bonded with a suitable glass fabric that has beenimpregnated with a fused organosol material. Optionally there may be afluoropolymer layer bonded to the other side of the impregnated glass inwhich case an optional primer layer would be required. Commerciallyavailable examples of suitable materials for this embodiment are setforth below:

FAA Soft Touch Film specification 1 2 3 4 5 6 7 8 OSU Peak  65 62  76 5359 71  43  49  53 Heat kw/m² Release Total  65 51  50 49 44 37  44  37 42 kw × min/m² Smoke Ds 200 99 126 94 97 86 104 121 100 4 min

The soft touch film is a grade of Aerofine available from Akzo Nobel,preferably the 8901 that is 2.5-2.7 mils thick and is composed of apolyurethane over a PVC base. The glass fiber is sold as 7628 Greigeglass from BGF. The middle PVC layer was S1670 sold by Spectrum. Theprepreg was S1687 sold by Spectrum. The acrylic primer is 68080 aflexible product adhesive sold by Dupont.

In another embodiment of the present invention the laminate comprises atop layer of clear urethane/polycarbonate film bonded to a clearPVDF/acrylic film containing fire retardants which is then bonded to aPVC layer containing pigments and flame retardants. These layers arebonded with a suitable adhesive to a fire resistant silicone foam/glassfabric. Optionally there may be a fluoropolymer layer between the PVClayer and the silicone foam.

Referring to FIG. 1, in this embodiment the laminate comprises a top plyof a clear layer that is about from 0.5 mil to about 3 mil of a flameretarded multiblock copolymer on a poly(vinyl halide) or apoly(vinylidene halide) layer. Suitable films are, for example sold asAerofine 8900 by Akzo Nobel. Optionally bound to the top ply using asuitable primer up to 0.5 mil in thickness. The prior materials are thenbonded to a PVC layer that is 1 to 25 mil in thickness which can befoamed or unfoamed. An organosol impregnated glass fabric is optionallybound to the PVC layer, wherein the glass fabric weighs from about 1 toabout 10 oz/yd², and the organosol is fused. A fluoropolymer layer (PVFor PVDF) such as Tedlar® offered by Dupont or Fluorex® products offeredby Akzo Nobel is optionally indirectly bonded to PVC, indirectly as aprimer layer is required to be used in conjunction with the optionalfluoropolymer layer. The fluoropolymer layer is preferably from about0.5-3.0 mils thick. An adhesive layer is then bonded as the final layer;the adhesive layer is preferably 1 to 5 oz/yd².

Referring to FIG. 3, in this embodiment the laminate comprises a top plyof clear 1.0-3 mil urethane/polycarbonate film. Suitable films aremanufactured by Akzo Nobel. Bound to the top ply using a suitableadhesive, such as Dupont 68080 adhesive primer, is a 0.8-1.5 mil clearPVDF/acrylic film containing fire retardants such as Airfilm LHR (LowHeat Release) offered by Schneller. The prior materials are then bondedto a fluoropolymer layer (PVF or PVDF) such as Tedlar® offered by Dupontof Soliant products offered by Akzo Nobel. The fluoropolymer layer ispreferably from about 0.5-2.0 mils thick. A silicone foam with glassbacking is bound to the fluoropolymer layer using a suitable adhesivesuch as HA 211 from Schneller. In one embodiment the silicone foam is 63mils thick. Suitable silicone foams can be purchased from RogersCorporation under the brand Bisco®.

Referring to FIG. 4, in this embodiment the laminate comprises afluoropolymer backing such as PVDF or PVF onto which a PVC material from2-10 mils in thickness is applied. The PVC can be calendared, extrudedor coated; it may contain pigments for coloration and fire retardants.In some instances it may be comprised of a couple of different layers ofPVC and some or all of it may be foamed. A top ply of 0.1-0.5 milspolyurethane/silicone is applied to the PVC.

Table 1 below sets forth the desired characteristics for the laminatesof the present invention including relevant regulations whereapplicable.

Laminates of the present invention can be applied by any suitable means.In certain instances they may be vacuum formed into place using meansknown in the art or applied using rollers or other means of exteriorpressure.

One of skill in the art will appreciate that a substantial degree ofdeviation from the processes and materials described herein is possibleand still be within the spirit of the invention.

TABLE 1 Targets plus team inputs Test method Characteristics 1 WithPressure Adhesion (ISO 4578) and sensitive adhesive burn (FAA),65/65/200 and 2 With Heat active FAA and OEM toxicity adhesives 3Resistance to AIMS 04-09-000, AIMS cleaning agent 04-09-001 and typicalDurability house cleaning agents 4 Tensile and elongation ISO min. 70N.60 to 80% 527 5 Tear ISO 4674 min. 0.8N 6 Dimensional changes less than1.5% change AIMS 04-09-000 after 75° C. for 24 h. 7 Taber weight loss.ISO 10 to 20 mg loss 9352 8 Five fingers scratch or visually as good asASTM 7027 our laminates 9 60 sec Vertical FAR 25.853 150, 10, 0 Burn 10NBS smoke <200 density 11 OSU Peak/total: 65/65, all substrate and alladhesives 12 Toxicity ABD 0031, vs Boeing Hydrogen Fluoride < D6-51377100/200 ppm Hydrogen chloride < 150/500 ppm Hydrogen cyanide < 150/150ppm Sulfur dioxide < 100/100 ppm Nitrous gases < 100/100 ppm Carbonmonoxide < 1000 ppm

What is claimed is:
 1. A laminate material comprising: a) a top layercomprising at least one layer of a multiblock copolymer comprising afirst layer of a cross-linkable thermoplastic or thermoset copolyamide,copolyester, styrenic or polyurethane; b) a bottom layer comprising atleast one layer of a poly(vinyl halide) or a poly(vinylidene halide), aprimer layer adjacent the at least one layer of a poly(vinyl halide) ora poly(vinylidene halide), at least one layer of PVC and at least oneimpregnated glass fabric layer on the bottom of the at least one layerof PVC, a primer layer adjacent the at least one impregnated glassfabric layer, and at least one layer of a poly(vinyl fluoride) or apoly(vinylidene fluoride) adjacent the impregnated glass fabric layer;and wherein the laminate further comprises at least one flame retardantand has an OSU Heat Release Total value of <65 kW min/m² and an OSU HeatRelease Peak value of <65 kW/m².
 2. The laminate material of claim 1further comprising an adhesive layer on the bottom of thepoly(vinylfluoride) or poly(vinylidene fluoride) layer.
 3. The laminateof claim 1 in which the bottom layer further comprises at least onelayer of a poly(vinyl fluoride) or a poly(vinylidene fluoride) adjacentthe primer layer adjacent the at least one impregnated glass fabriclayer.
 4. The laminate of claim 1 further comprising at least one flameretardant selected from the group consisting of hydrated aluminas,magnesium hydroxide, phosphate ester plasticizers, tetrabromophthalates,tetrachlorophthalates, chlorinated hydrocarbons, ammonium octamolybdate,alkyl aluminum phosphonates and phosphinates, zinc sulfides, zincborates, zinc hydroxy stannates, and bismuth oxide.
 5. A laminatematerial comprising: a) a top layer comprising at least one layer of amultiblock copolymer comprising a first layer of a cross-linkablethermoplastic or thermoset copolyamide, copolyester, styrenic orpolyurethane; and b) a bottom layer comprising at least one layer of apoly(vinyl halide) or a poly(vinylidene halide), at least one layer of aPVC adjacent the at least one layer of a poly(vinyl halide) or apoly(vinylidene halide) and at least one layer of a poly(vinyl fluoride)or a poly(vinylidene fluoride) adjacent the layer of PVC.
 6. Thelaminate of claim 5 wherein, the bottom layer further comprises a primerlayer adjacent the at least one layer of a poly(vinyl halide) or apoly(vinylidene halide).
 7. The laminate material of claim 6 furthercomprising a primer layer adjacent adhesive layer on the bottom of thepoly(vinylfluoride) or poly(vinylidene fluoride) layer.
 8. The laminatematerial of claim 6 further comprising at least one primer layeradjacent the at least one layer of a poly(vinyl fluoride) or apoly(vinylidene fluoride).
 9. The laminate material of claim 8 furthercomprising an adhesive layer on the bottom of the at least onepoly(vinylfluoride) or poly(vinylidene fluoride) layer.
 10. The laminateof claim 5 further comprising an adhesive layer on the bottom of the atleast one poly(vinylfluoride) or poly(vinylidene fluoride) layer. 11.The laminate of claim 10 further comprising at least one layer of primerabove the at least one poly(vinylfluoride) or poly(vinylidene fluoride)layer.
 12. The laminate of claim 5 further comprising at least one layerof primer above the at least one poly(vinylfluoride) or poly(vinylidenefluoride) layer.
 13. The laminate of claim 5 further comprising at leastone the flame retardant selected from the group consisting of hydratedaluminas, magnesium hydroxide, phosphate ester plasticizers,tetrabromophthalates, tetrachlorophthalates, chlorinated hydrocarbons,ammonium octamolybdate, alkyl aluminum phosphonates and phosphinates,zinc sulfides, zinc borates, zinc hydroxy stannates, and bismuth oxide,and the laminate having an OSU Heat Release Total value of <65 kW min/m²and an OSU Heat Release Peak value of <65 kW/m².